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ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
http://www.e-journals.net 2009, 6(3), 659-664
Photosensitization Studies in Selected Dyestuffs
VIKESH KUMAR, M.R.TRIPATHI*,
MANISH KUMAR and GOPAL SHUKLA
Department of Chemistry,
D.A.V.P.G. College, Kanpur 208001 Uttar Pradesh, India.
tripathimadhoram@yahoo.co.in
Received 20 November 2008; Accepted 1 January 2009
Abstract: There are various dyestuffs species to produce reactive oxygen
such as singlet oxygen O2 and super oxide radicals. Irradiation with sun
light in vitro, the dyestuff like benzanthrone, metanil yellow and p-
aminodiphenylamine were found to produce reactive oxygen species such
as singlet oxygen (1O2) and/or superoxide radicals (O2-). However
benzanthrone produces detectable amount of 1O2 Although metanil yellow
and p-aminodiphenylamine (p-ADPA) did not produce detectable amounts
of 1O2 under similar conditions. The above dyestuffs are routinely used in
textiles, cosmetics, detergents, leather industries as well as food additives.
In view of the fact that workers exposed to some of these chemicals during
manufacture, pulverization and storage develop edema and even skin
cancers in the exposed areas of skin. We believe that activated oxygen
species may play a major role in the development of these symptoms.
Keywords: Dyes, Benzanthrone, Photosensitization, Singlet oxygen, Superoxide radicals.
Introduction
Production of synthetic dyes in India is about 25000 metric tons every year1. Which are
Industrial health hazards to people2. Dyestuff industries have occupied a prominent place
in the industrial organization of the modern world. One of the major routes to incorporate dyestuffs in our biological system is by absorption through skin. Some dyes have different degrees of binding ability with protein, collagen and lipids
3-4. Study shows that
toxic effect of these synthetic dyes are observed in the presence of the ultraviolet component of sunlight (285-400 nm)
5. Photosensitization reactions in our analysis is
oxygen dependent in which a photo excited dye transfers energy to molecular oxygen to produce activated oxygen species like singlet oxygen (
1O2), super oxide radical (HO2 or
(O2-), hydroxyl radical (OH) and hydrogen peroxide. The activated oxygen species
contribute to oxidative degradation of protein, enzymes, lipids and other target
660 M. R. TRIPATHI et al.
molecules of cellular systems6-8
and are also responsible to act as tumor promoters in the development of cancer
9.
In present study the reason for taking benzanthrone (7H-benz(de)anthrance-7-one)
is used in the synthesis of many vat and disperse dyes. It has been observed that workers
coming into contact with it during manufacture, pulverization and storage develop
itching, burning sensation, erythema, roughness, dryness and pigmentation of the
skin10-11
. Orange II [monoazo, C.I. acid yellow, orange 7 (15510)], a sodium or calcium
salt of p-(2-hydroxyl-1-naphthalenyl) azo benzenesulfonic acid is used in dyeing of
paper, soaps etc12
. A blend of orange II with metanil yellow under the trade name to
cause deleterious effects in our biological system13
. Metanil yellow [monoazo, C.I. acid
yellow 36 (13065)], a sodium or calcium salt of m-(p-anilinophenyl-azo)
benzenesulfonic acid, is used in the coloring of foodstuffs, soaps, shoe polishes, wood
stains, paper staining and cosmetics. p-Aminodiphenylamine (p-ADPA) and metanilic
acid are important metabolites of metanil yellow14
and are considered to be an active
ingredient of metanil yellow induced toxicity15
. p-ADPA is used as an intermediate for
the synthesis of photographic chemicals, and the manufacture of dyeing reagents16-17
. It
is also used as an ingredient in oxidizing types of hair dyes18
. Its properties of skin
irritation and sensitization are well known19
.
Experimental
Benzathrone was obtained from Kalyan Dye Stuff Industry, Kalyan, Bombay. Metanil
yellow and orange II were obtained from M/s Vsco Products Pvt. Ltd., Metanilic acid and
nitro blue tetrazolium (NBT) were procured from Sisco Research Lab, Bomaby.
1,4-Diazabicyclo- (2,2,2)-octoane (DABCO), p-ADPA, superoxide dismutase (SOD) and
N, N-demethyl-p-nitrosoaniline (RNO) were obtained from Sigma Chemical Co., U.S.A.
Sodium azide and histidine (HIS) were obtained form HiMedia Lab., Bombay. Other
chemicals and solvents used throughout the study were of analytical grade and obtained
form E. Merck- BDH Chemical Company. The dyes were further purified by column
chromatography.
Ultraviolet and visible spectra were recorded on a Shumatzu 450 UV/visible
spectrophotometer using quartz cells of 5 cm path length. Irradiation experiments were
done as follow: 10-mL solutions were taken in a Petri dish (6 cm diameter) and
irradiated with direct sunlight. The temperature was maintained at 20+2 0C by using a
constant temperature water bath. Irradiation experiments were done in Kanpur, U.P. on
sunny days preferably between 9:00 and 11.00 am. The irradiance of emitted light was
measured by an International Light IL-730 UV Actinic Radiometer (International Light
Company, Newburyport, Mass., U.S.A.) equipped with a calibrated and cosine-
corrected ultraviolet radiation detecting probe. Sunlight produced an average
ultraviolet radiaton of approx. 1.2+0.1×102 erg. mm-2
. s-1
in the UV-A range (320-400
nm). It also produced approx. 1.0+0.1×10-4
erg. mm-2
. s-1
of UV-B (285-320 nm)
radiations under similar conditions. The results of intensity measurement were also
confirmed by chemical actinometry20
. Formation of 1O2 was determined in aqueous
solutions by the method of Kraljic and Mohsini21
. With water insoluble chemicals,
reactions were done in dimethyl formamide (DMF) solution (5-20% in 0.01 M
phosphate buffer, pH 7). A 10 mL solution of RNO was prepared in a phosphate buffer
(0.01 M, pH7) and optical density was adjusted between 1.2 and 1.4. Histidine (1×10-2
M)
was added to the RNO solution as a selective acceptor of 1O2. Stock solutions (1 mg/mL)
Photosensitization Studies in Selected Dyestuffs 661
of test compounds were prepared in ethanol, DMF or dimethyl sulfoxide (DMSO).
RNO and HIS samples were irradiated with various concentrations of test compounds
(0.1, 1.0 and 10 µg/mL) and sunlight dose (0-40 min). Singlet oxygen forms a
transannular peroxide intermediate with HIS leading to the bleaching of 1O2 was also
established by examining the reaction kinetics in D2O and by carrying out quenching
studies with sodium azide22
and DABCO23
. Solvents like D2O and C2H5OH are known
to prolong the life time of singlet oxygen24
. Formation of (O2-) was studied by
monitoring the photosensitized reduction of NBT25
with some modifications.
Reduction of NBT by (O2-) leads to the formation of a blue coloured product (nitro blue
formazan), which is quantitatively estimated spectrophotometrically at 560 nm.
A 1.67×10-4
M solution of NBT was prepared in carbonate buffer (0.01 M, pH 10)
containing 10-20% DMF to keep the reaction product in solution. 10 mL solutions
were irradiated with various concentrations of test samples in sunlight for varying
lengths of time. Further evidences for the generation of (O2-) were obtained by
performing quenching studies with SOD26
.
Results and Discussion
Singlet oxygen production
A comparative study of the 1O2 producing ability of various dyes is summarized in
Table 1. Only benzathrone was found to generate sufficient 1O2 to be monitored
spectrophotometrically by a drop in optical density at 440 nm due to bleaching of RNO
by the transannular peroxide intermediate of HIS and 1O2. The
1O2 generating potential
of benzathrone was comparable to well known photosensitizing agents like anthracene.
Dose-response relation
The formation of 1O2 from benzathrone was found to be both concentration and sunlight
dose-dependent. A nearly linear relationship was found between the concentration of
benzathrone (1- 10 µg/mL) and the amount of 1O2 produced after 15 min exposure with
sunlight (Figure 1). The study was done using a 10 µg/mL concentration of benzanthrone.
The relationship between 1O2 production and concentration of test compound was observed
in dilute solutions only. At higher concentration the linearity was disturbed due to low
solubility of benbzanthrone as well as low penetration of solar radiation into the colloidal
irradiation solution.
Super oxide radical’s production
It was interesting to know that metanil yellow and p-aminodiphenylamine, the two dyes
which gave a negative test for 1O2, were found to produce (O2
-) in appreciable yields (Table 1
& Figure 3). Benzanthrone produced (O2-) in almost the same quantity as produced by
anthracene and hematoporphyrin27
. p-Aminodiphenylamine produced (O2-) comparable to
benzanthrone, whereas metanil yellow produced lower amounts of (O2-) in comparison to its
metabolite. Metanilic acid, orange II and sulfanilic acid did not produce detectable amounts
of (O2-) under similar conditions.
Selected dyes and dyestuffs, benzanthrone, orange II, metanil yellow and p-ADPA most
commonly used in colouring and textile industries as well as food additives were examined
for their ability to produce activated oxygen species [1O2 and (O2
-)] under normal sunlight
with a view to investigating the possible occupational health hazard to people through a
series of photodynamic oxidation reactions leading to cell damage.
662 M. R. TRIPATHI et al.
Figure 1. Production of singlet oxygen by benzathrone 1-10 µg/mL upon sunlight 15 min as
measured by recording a decrease in UV-absorption of RNO (32±0.2x10-5
M in 0.01 M phosphate
buffer with 20% DMF, pH 7) containing HIS (1x10-2 M) as a selective acceptor of
102.
Figure 2. Relationship between the production of 0-2
and concentration (0-20 µg/mL) of the
following: 1, metanil yellow; 2, p-ADPA: and 3, benzathrone.
Table 1. A comparison of chemical agents tested for 1o2 and (O2
-) production.
Chemicals* 1O2 production (O2
-) production
Benzanthrone Mild Mild
Metanil yellow ND Mild
p-ADPA ND Mild
Concentration, µg/mL
0- 2
µM
Concentration, µg/mL
∆O
. D
. A
t 4
40
nm
Photosensitization Studies in Selected Dyestuffs 663
The formation of 1O2 by benzanthrone and (O2
-) by metanil yellow, p-ADPA and
benzanthrone might rise several question about their safety particularly in conjugation with
exposure to sunlight. Studies shows that, exposure to metanil yellow, p-ADPA and
benzanthrone may lead to various short and long term skin photosensitization and cell
damaging effects.
Photosensitized reactions of dyes leading to the formation of activated oxygen species
are believed to be a matter of great concern because the later are involved in the destruction
of cells, tissues, phagocytes and certain cancer inducing processes5,7,9,11
. Moreover, Bickers
et al28
have demonstrated the destruction of epidermal cytochrome P-450 in epidermal
microsomes by 1O2 generated through photosensitization reactions induced by
hematoporphyrin derivatives. Several other studies have also suggested that 1O2, (O2
-) and
other reactive forms of oxygen play a major role in the UV-induced membrane damaging
reaction29-30
.
Although spectroscopic studies of cutaneous photosensitizing agent XVII benzanthrone
were carried out by Reza Dabestani et al31
. The important roles of reactive oxygen species in
diseases related to aging and the necessity and benefits of antioxidative netraceuticals in
prevention of disease and promotion of healthy aging reported in the recent years32-34
.
Conclusion
Analysis was carried out of above dyes at concentration range of (1-10 µg/mL) and exposure
period. At higher concentration the linearity was disturbed due to lack of penetration of solar
radiation through the colloidal system.
References
1. Fernando A C, Kothari's Economic & Industrial Guide of India, 34th
Ed., Chemicals
& Pharm., Kothari & Sons, Madras, India. 1982/83, 6-7.
2. Munn A and Smagghe G, Encyclopaedia of Occupational Health and Safety
(Parmeggiani, L., Ed.), International Labour Organization, Geneva III. Ed., 1,
1983, 699.
3. Joshi A, Khanna S K, Singh G B and Krishnamutri C R, Industrial Health, 1982, 20,
305-313.
4. Joshi A, Khanna S K, Singh G B and Krishnamutri C R, J Biosci., 1981, 3, 379-388.
5. Parrish J A, Anderson R R, Urbach F and Pitts D, UV-A, Biological Effects of
Ultraviolet Radiations with Emphasis on Human Responses to Longwave
Ultraviolet, Plenum Press, New York, 1978.
6. Prayer W A, Free Radicals in Biology, Academic Press, New York, 1976, 2, 85-133.
7. Krinsky N I, Singlet Oxygen (Wasserman H H and Murray R W, Eds.) Academic
Press, New York, 1979, 597-667.
8. Joshi P C, Toxicol Lett., 1985, 26 ,211-217.
9. Marx J L, Science, 1983, 219, 158-159.
10. Trivedi D H and Niyogi A K, Indian J Indust Med., 1968, 14, 13.
11. Singh G B and Zaidi S H, J Ind Med Assoc.,1969, 52 , 558-560.
12. Gurr E, Synthetic Dyes in Biology, Medicine and Industry, Academic Press, New
York, 1971, 237.
13. Singh G B and Khanna S K, Indian J Exp Biol., 1979, 17, 1100-1102.
14. Srivastava L P, Khanna S K, Singh G B and Krishnamurti C R, Environ Res., 1982,
27, 185-189.
664 M. R. TRIPATHI et al.
15. Raza H, Biochemical Studies on Some Food Dyes, Ph.D. thesis submitted to Kanpur
University, India, 1980.
16. Uniroyal Chemicals, p-Aminodiphenylamine, Naugatack (R) Chemicals, Division
of Unioryal Inc, Naugatack C K, 1976.
17. Color Index, The Society of Dyers & Colourists, England and The American
Association of Textile Chemicals & Colorists, U.S.A., 1971, 2, 2002.
18. Wall F E, Cosmetics Science and Technology (Balasam M S and Sagarin E, Eds.),
Wiley, New York, 1972, 2, 306.
19. Szamarch H, Przeglad Dermatol., 1966, 53, 445-452.
20. Hatchard C G and Parker C A, Proc R Soc London, 1956, 235, 518-536.
21. Kraljic I and El Mohsni S, Photochem Photobiol., 1978, 28, 577-581.
22. Foote C S, Fugimoto T T and Chang Y C, Tetrahedron Lett., 1972 ,45-48.
23. Quannes C and Wilson T J, Am Chem Soc., 1968, 90, 6527-6528.
24. Kearns D R, Singlet Oxygen (Wasserman H H and Murray R W, Eds.), Academics
Press, New York, 1979, 115-137.
25. Korycka-Dahl M and Richardson T, J Dairy Sci., 1977, 61, 400-407.
26. McCord J M and Fridovich I, J Biol., 1969, 244, 4049-6055.
27. Joshi P C and Pathak M A, Biochem Biophys Res Commun., 1983, 112, 638-646.
28. Bickers D R, Dixit R and Mukhtar H, Biochem Biophys Res Commun., 1982, 108,
1032-1039.
29. Ito T, Photochem Photobiol., 1978, 28,493-508.
30. Anderson S M, Krinsky N I, Stone M R and Clagett D C, Photochem Photobiol.,
1974, 20, 65-69.
31. Robert H Sik, Photochem Photobiol., 1992, 55(4), 533-539.
32. Galey J B, Int J Cosmet Sci., 1991, 13(2), 65-78.
33. Riley P A, Int J Radiat boil., 1994, 65(1), 27-33.
34. Lee J, Koo N and Min D B, Comprehensive reviews in food science and safety
2004, 3(1), 21-33.
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